Functional perfluoroalkylene organosilicon compounds

ABSTRACT

SILOXANES CONTAINING AT LEAST ONE UNIT OF THE FORMULA   X-RF-(CH2-CH2)N-CH2-CH2-SI(-R&#34;)M-O((3-M)/2)   FOR EXAMPLE,   -SI(-CH3)(-CH2-CH2-(CF2)2-COO-C2H5)-O-   ARE DISCLOSED AS LUBRICANTS, LAMINATING RESINS, ELASTOMERS AND SURFACE ACTIVE AGENTS.

United States Patent O 3,560,542 FUNCTIONAL PERFLUOROALKYLENEORGANOSILICON COMPOUNDS Yung Ki Kim and Ogden R. Pierce, Midland, Mich.,as-

signors to Dow Corning Corporation, Midland, Mich., a corporation ofMichigan No Drawing. Original application Dec. 2, 1966, Ser. No.598,613, now Patent No. 3,478,076. Divided and this application Aug. 1,1969, Ser. No. 846,924

Int. Cl. C07f 7/08; C08f 11/04; Cm 1/50 US. Cl. 260-4482 4 ClaimsABSTRACT OF THE DISCLOSURE Siloxanes containing at least one unit of theformula are disclosed as lubricants, laminating resins, elastomers andsurface active agents.

CROSS REFERENCES TO RELATED APPLICATIONS This application is a divisionof copending application Ser. No. 598,613, filed Dec. 2, 1966, now US.Pat. 3,478,- 076.

The intermediates for the preparation of the compositions of thisinvention are described and claimed in the copending application Ser.No. 598,604, of Yung Ki Kim entitled Fluoroethylene Compounds, filedDec. 2, 1966, now US. Pat. 3,503,945. The disclosure of said applicationbeing hereby incorporated in this application by reference.

BACKGROUND OF THE INVENTION This invention provides the art with newfunctional organosilicon compounds in which the functions are ester,carboxy, amide, etc. The unique feature being the bridge connecting saidfunctional groups to the silicon atom. The organic functional group isattached directly to a perfiuoroalkylene radical, which in turn, isconnected to the silicon through an ethylene spacer. The ethylene spacerstabilizes the compounds to hydrolytic cleavage because fluorineattached to carbon atoms alpha or beta to silicon is unstable.

SUMMARY OF THE INVENTION This invention relates to siloxanes having atleast one unit of the formula in which Y is a hydrolyzable group orOI-I;

R" is a monovalent hydrocarbon radical free of aliphatic unsaturated ora ACH' CH radical in which A is a perfluoroalkyl radical;

m and it each have values of from O to 2 inclusive;

R is a perfluoroalkylene radical;

X is a radical of the group COOH, CONH CEN and COOR' in which R is analkyl radical of 1 to 6 inclusive carbon atoms; and

Patented Feb. 2, 1971 b has a value from 0 to 2 inclusive, any remainingunits in said siloxane being of the formula a has a value from 0 to 3inclusive.

DETAILED DESCRIPTION OF THE INVENTION The silanes precursors for theabove-described siloxanes are best prepared by reacting silanes of theformula R/Im Yss iH with (I) CH. =CH(CH CH ),,R X' in the presence of aplatinum catalyst such as chloroplatinic acid in the conventional mannerfor adding SiH compounds to compounds having the terminal CH CH group.The olefinic intermediates (1) are prepared in accordance with thedescription of the aforesaid copending application of Yung Ki Kim.

The silanols (i.e. where Y is OH) are best prepared by hydrolyzing thecorresponding hydrolyzable silanes under neutral conditions by any ofthe methods well known in the art for the preparation of silanols. Thepreferred method for preparing such silanols is by the hydrolysis ofthose compounds in which Y is methoxy.

The siloXanes of this invention can be prepared by two methods. One isby the hydrolysis or cohydrolysis of the above silanes, by conventionalmeans, or by the cohydrolysis of the above defined silanes with silanesof the formula Z SiY in which Z, a and Y are as above defined. Theparticular method chosen for the hydrolysis or cohydrolysis can varywidely depending upon the nature of the substituent groups on thesilicon. Hence there are no critical conditions other than thewell-known techniques for hydrolyzing and cohydrolyzing silanes.

A second method of preparing such siloxanes is by the addition ofcompounds (I) supra to siloxanes containing SiH groups in the presenceof platinum catalysts. The conditions for carrying out this reaction arethose normally employed for the addition of SiH containing siloxanes toolefins.

In those siloxanes in which X is a carboxyl group it is preferred thatsuch compounds be prepared by the hydrolysis of the correspondingesters, i.e. hydrolysis of R".,, ROOCRKCHgClIzMCHzCHzSiYHn or ofsiloxanes containing units of the formula In general, better yields ofthe carboxylic acids are obtained by this method than by attempting toadd unsaturated carboxylic acids directly to SiH compounds. Thehydrolysis of the esters can be carried out in the conventional mannerfor the hydrolysis of organic esters.

In the compositions of this invention Y can be any hydrolyzable groupsuch as halogen atoms; such as fluo rine, chlorine or bromine;hydrocarbonoxy groups such as methoxy, ethoxy, octadecyloxy, allyloxy,cyclohexyloxy, phenoxy, tolyloxy, benzyloxy, OCH CH OCH and acyloxygroups such as acetoxy, propionyloxy, benzoyloxy, cyclohexoyloxy, and

ketoxime groups such as ON=C(CH and fONQ amine groups such as NH N('CHand sulfide groups such as SCH and the nitrile groups, the isocyanategroup, sulfate groups such as H -O i 0 02115 sulfonate groups such ascarbamate groups such as OOCNHCH -OOCN(CH R can be any perfiuoroalkyleneradical such as 2": 2 2', 2) 1s= R can be any lower alkyl radical suchas methyl, ethyl, isopropyl or hexyl.

As can be seen the silioxanes of this invention can be homopolymers orthey can be copolymers containing various types of the fluoroalkylenecontaining siloxane units. When Q represents group XR (-CH CH ),,CH CHthe siloxanes of this invention can be represented by the general unitformulae R" R"2 Y2 QSiOa/z, QS iO, As iolli', QS iO, s'io and or anycombination thereof. In addition the siloxanes can contain siloxaneunits of the formula in which a has a value of from 0 to 3 inclusive.

This includes units of the type SiO ZSiO Z SiO, Z SiO1 2.

Z can be a hydrogen atom, any of the above defined Y groups, a hydroxylgroup or any hydrocarbon radical such as any of the radicalsspecifically shown for R" above, divalent hydrocarbon radicals such asalkylene radicals such as methylene, dimethylene, trimethylene, ortetramethylene; arylene radicals such as phenylene, Xenylene, tolylene,xylylene or naphthylene; and cycloalkylene radicals such ascyclohexylene and cyclopentylene. Z can also be any alkenyl radical suchas vinyl, allyl, hexenyl and butadienyl.

Z can also be any halohydrocarbon radical such as chloromethyl,gamma-chloropropyl, bromooctadecyl, chlorocyclohexyl, bromocyclohexenyl,3-chlorobutenyl-4, chlorophenyl, bromoxenyl, t1,0t,OL-tIlflllOl'OtOlyl,tetrachlorophenyl, p-chlorobenzyl, 3,3,3-trifiuoropropyl and C F -CH CHThe compositions of this invention are useful for a wide variety ofapplications. These include oleophobic coatings, lubricants for metallicparts, elastomers, laminating resins, and surface active agents.

The following examples are illustrative only and should not be construedas limiting the invention, which is properly delineated in the appendedclaims.

EXAMPLE 1 To a mixture of 150 grams (.75 mole) of CH =CH(CF COOC H and.75 milliliter of chloroplatinic acid in absolute ethanol was added atotal of 0.85 mole of methyldichlorosilane as follows: 10 grams of thesilane was added and the mixture was stirred and heated. When thetemperature reached C. the reaction started and heating was discontinuedwhen the temperature reached C. The remaining silane was then added atsuch a rate that the temperature was maintained between 110 and C. Theentire reaction was carried out in an atmosphere of dry nitrogen.

The crude product was distilled to give the compound 021150 00 (C F22CH2CHzSlCl2 the boiling point 120 C. at 20 millimeters and refractiveindex at 25 C. of 1.4065.

A portion of this silane (30 grams) was added with stirring to a mixtureof 200 milliliters of water and.30 grams of sodium bicarbonate. Thereaction was carried out at ice bath temperature. The mixture was takenup in ether and the ether layer was separated, washed and dried. Thesolvent was evaporated to give a clear 'viscous oil which containedsilicon-bonded hydroxyl groups, i.e. units of the formula Alla 091150 00(0 Fg)gOH2CH2S iO1/2.

The oil was mixed with tetra-methyl guanidine acetate and heated undervacuum for 24 hours at 75 to C. Water was removed during thepolymerization. A viscous siloxane fluid was obtained which had the unitformula i C2H OOC(CFg)gCHzGHzSiO.

EXAMPLE 2 When the following fluoroalkylene compounds are added to thefollowing silanes in accordance with the procedure of Example 1, thefollowing products are 6 obtained:

Fluoroalkylene compound Silune Product CH2=CH(OF2)2CONH2 HSiO(C2Hs)3 (1)H2NOO(C F:|)2CH2CH2S1(OC2II5)3 3 CH OH2=CHCH2CH2(CF2)2O0OO2H5 HiClz (2)C:H OOC(CF2)2(CHz)4S iCl (CH3)2 (CHa)2 CH2=CH(CF2)2CEN HSiCl (3)NEC(CF2)ECH CH2SlC1 CuHs Cn B OH =CH(CF2) COOCH 3 HSiClg (4)HmCuOOC(CF2)5CH2CHzSlClg CIBHLW C1s a1 CHFCH(CF2)ISCOOCH3 HS KOOGCH M(5) CI'IKOOC(CF2 18CH2CH2S1(OOCCII3)2 OHFCH(CH2CH2)2 CFQ)2CENHSi(ON=C(CHs)2ln (6) NT C(CF2)2(CH2)tSi[ON=C(CH CHzCHzCF: CHZCH CFOIIQZCI'ICFCFECOOC2H5 HSi(OOCN(CH3)2[z (7) CHsOOCCF2CF(CH2)zSi{OOCN(OHs)2l2 LFa 6F;

EXAMPLE 3 and cohydrolyzed as shown below the following siloxanes Whenthe silane products of Example 2 are hydrolyzed are obtained. Theproportions are in mol percent.

fii li iz r n gl li Other silanes Reagent Siloxane produced (1) 1 wt.percent aqueous acetic acid HzNC(GF CH2CH SiO CH (2) te 2 50OC(Fz)z(CHz)4 slO (a) --d Nzcw 1%,013no1ansxo Copolymer of:

50% (4) 50% H C OOC(OF CH OH SiO "down-hnnnnunh" 15 31 CHQOOC (CFghgCHzCHzSiO 25% NEC (C Fz)g(CH2)flSiO3/2 Copolymer of:

25% (orm suoomn. %gg (O 2)2C zCHzSiOaN gliiiglttlfzfiggjjjjji percentaqueous H01 Ca n i(O 2 5)3 H i fi' O3/2 03/2 Copolymer of:

9% CF3CH2CH2S1C13 u 1% 2)2 2 2 0r5 3)z 1% (3) c msic Water gg gsg fimmlz 25% 0113519154.". ani/( 25% Cmaslch 25% C H SiO CH; 30% O HaO 0C(OF(GH2)4 3iO 0 11 a l 30% (2) 10% ()Hasiclz Odo n 13 5: 2)e s 2 0 CH3 l30% 4 30% on2=o ClOfizCHzSiClz 10% CH! S10 CH i30% OHFOClCHzCHz iO 2 s)4Nzcwmhmhofizsio S1 25% 1) 75% (CHahSiC ..do 2NOC(CFzhCHzCH Si[OSi(CH (2)10 molperc nt theory water 11562000) mm); (OH (OF COOC H 01 Cl Si 0 S1 C3 C 3 n (4) Aqueous ammonia at 30 C HIQOGO O C (C F2)|}CH2OH2S1(OI{)2*Average formula.

EXAMPLE 4 When the siloxane ester CH O2H5OOC(OF2)2(CH2)41O is hydrolyzedwith aqueous HCl under refluxing conditions the siloxane noocwrmwnmiiois obtained. This siloxane can also be obtained by reacting the siloxaneester with an equivalent amount of acetic acid in the presence of acatalytic amount of HCl under conditions where ethylacetate distillsfrom the mixture.

EXAMPLE 5 54 grams of CH =CHCF CF COOC H was placed in a flask togetherwith .3 milliliter of a .1 mol solution of H PtCl -H O in ethanol. T othe mixture was added with stirring 40.1 grams of HSiCl The silane wasadded slowly at a temperature of 100 to 115 C. The reaction was carriedout under N After stirring overnight the mixture was distilled to give CH OOOCF CF CH CH SiCl boiling point 98 C. at 6 millimeter, 11 1.4080.

When this material is hydrolyzed a resinous siloxane of the unit formulaC H OOCCFgcF CH cH SiO is obtained.

That which is claimed is:

1. A siloxane having at least one unit of the formula in which X is ofthe group consisting of COOH, CONH CEN and COOR', in which R is an alkylradical of from 1 to 6 inclusive carbon atoms;

R, is a perfluoroalkylene radical of from 1 to 18 inclusive carbonatoms;

In and m each have values from 0 to 2 inclusive;

R" is a monovalent hydrocarbon radical selected from the groupconsisting of alkyl radicals, cycloaliphatic radicals, aromaticradicals, aralkyl radicals or ACH CH radicals in which A is aperfluoroalkyl radical; Y is a hydrolyzable radical or an -OH, and b hasa value from 0 to 2 inclusive; any remaining siloxane units being of theformula ZsSiO in which Z is selected from the group consisting of thehydrogen atom, the hydroxyl group, hydrolyzable radicals, alkylradicals, halogenated alkyl radicals, cycloaliphatic radicals,halogented cycloaliphatic radicals, aromatic radicals, haloaromaticradicals, aralkyl radicals and haloaralkyl radicals and a has a valuefrom 0 to 3 inclusive.

2. A composition in accordance with claim 1 in which all of the unitsare of the Formula 1.

3. A siloxane in accordance with claim 2 in which X is --COOC H R: is CFCF n is 0, R" is CH m is 1, and b is 0.

4. A siloxane in accordance with claim 2 in which X is R 1S and n, m andb are each 0.

References Cited UNITED STATES PATENTS 3,038,000 6/1962 Schmidt260-448.2(B) 3,014,056 12/1961 Kerschner 260448.2(B) 3,450,738 6/1969Blochl 260448.2X 3,458,554 7/1969 Haluska 260448.2(B) 3,478,076 11/1969Kim et a1 260-448.2(B)

TOBIAS E. LEVOW, Primary Examiner P. F. SCI-IAVER, Assistant ExaminerUS. Cl. X.R.

